This is possible, but I would avoid it to prevent a bad customer experience of ringing to the desk of a rep who is not prepared.
To make this happen you would need to create a Workflow in architect based on the schema of the 'v2.users.{id}.activity' topic, specifically looking for the user to enter Available status. Then you would need to use a Data Action to run an API call that changes them from Available to OnQueue. Once you have a workflow to do this filter>update of status, you would create a Trigger in admin that runs the workflow based on the topic mentioned earlier. If you only want this for some users, ie not supervisors, you would want a data table or API call to a database to filter by user ID and not just status.
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Brad Murlin
Zillow, Inc.
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